Three of the 10 patients with SCI who were directly injected with autologous MSCs showed improvement in the motor power of the upper extremities and in activities of daily living, as well as significant magnetic resonance imaging and electrophysiological changes during long-term follow-up.
Transition-metal-catalyzed or metal-free azide-alkyne cycloadditions are methods to access 1,4- or 1,5-disubstituted 1,2,3-triazoles. Although the copper-catalyzed cycloaddition to access 1,4-disubstituted products has been applied to biomolecular reaction systems, the azide-alkyne cycloaddition to access the complementary 1,5-regioisomers under aqueous and ambient conditions remains a challenge due to limited substrate scope or moisture-/air-sensitive catalysts. Herein, we report a method to access 1,5-disubstituted 1,2,3-triazoles using a CpNi/Xantphos catalytic system. The reaction proceeds both in water and organic solvents at room temperature. This protocol is simple and scalable with a broad substrate scope including both aliphatic and aromatic substrates. Moreover, triazoles attached with carbohydrates or amino acids are prepared via this cycloaddition.
Sulfuryl fluoride gas is a key reagent for SO2F transfer. However, conventional SO2F transfer reactions have limited 18F-radiochemistry translation, due to the inaccessibility of gaseous [18F]SO2F2. Herein, we report the first SO2F2-free synthesis of aryl [18F]fluorosulfates from both phenolic and isolated aryl imidazylate precursors with cyclotron-produced 18F–. The radiochemical yields ranged from moderate to good with excellent functional group tolerance. The reliability of our approach was validated by the automated radiosynthesis of 4-acetamidophenyl [18F]fluorosulfate.
Synthesis of sulfamoyl [18F]fluorides has been a challenging topic owing to the inefficient nucleophilic radiofluorination of sulfamoyl derivatives. Herein, we report an 18F/19F isotopic exchange approach to synthesize various sulfamoyl [18F]fluorides, otherwise inaccessible via direct synthesis from amines, with high radiochemical yields up to 97% (30 examples). This late-stage labeling protocol offers an efficient route to yield functionalized molecules by diversifying the chemical library possessing sulfamoyl functionalities through nucleophilic 18F incorporation within nitrogen-containing sulfur(VI) frameworks.
Annulative π-extension chemistry provides a concise synthetic route to polycyclic arenes. Herein, we disclose a nondirected annulation approach of unactivated simple arenes. The palladium-catalyzed 2-fold C–H arylation event facilitates tandem C–C linkage relays to furnish fully benzenoid triphenylene frameworks using cyclic diaryliodonium salts. The inseparable regioisomeric mixture of 1- and 2-methyltriphenylenes is identified by the combined analysis of ion mobility-mass spectrometry, gas-phase infrared spectroscopy, and molecular simulation studies.
Impairing the division of cancer cells with genotoxic small molecules has been a primary goal to develop chemotherapeutic agents. However, DNA mismatch repair (MMR)-deficient cancer cells, are resistant to most conventional chemotherapeutic agents. Here we have identified baicalein as a small molecule that selectively kills MutSα-deficient cancer cells. Baicalein binds preferentially to mismatched DNA and induces a DNA damage response in a mismatch repair-dependent manner. In MutSα-proficient cells, baicalein binds to MutSα to dissociate CHK2 from MutSα leading to S phase arrest and cell survival. In contrast, continued replication in the presence of baicalein in MutSα-deficient cells results in a high number of DNA double-strand breaks and ultimately leads to apoptosis. Consistently, baicalein specifically shrinks MutSα-deficient xenograft tumors and inhibits the growth of AOM-DSS-induced colon tumors in colon-specific MSH2 knockout mice. Collectively, baicalein offers the potential of an improved treatment option for patients with tumors with a DNA MMR deficiency.
over geometry or function is needed at the molecular level. For instance, DAEs have been used to switch fluorescence on and off repeatedly in bioimaging. [5][6][7][8][9][10][11][12][13][14] Unlike irreversibly switchable fluorescence probes, [15][16][17] reversible fluorescence photoswitches can enhance the spatial resolution and accuracy of signals-even for images manifesting autofluorescence signals-via their rigorously controlled photo-responsive switching between ONand OFF-states. [18][19][20][21] This can be fulfilled, in terms of molecular design, either by placing a fluorophore and a DAE moiety (or multiple copies of each) nearby in the same molecule (e.g., a dyad) [5,8,9,11,14,21,22] so that fluorescence quenching is feasible through fluorescence resonance energy transfer (FRET) [23] or by using a DAE derivative alone that can fluoresce in its closed form (Scheme S1, Supporting Information). [10,[24][25][26] Recently, the latter type of fluorescence photoswitches, in particular, based on turn-on mode sulfone derivatives of DAE, [5,[24][25][26][27][28][29][30][31][32][33][34] has been intensively investigated for super-resolution imaging [5,27,29,30,[32][33][34][35][36] in aqueous solutions. [5,27,32,33] While some nanoparticulate fluorophores such as conjugated polymers [7,9] or quantum dots [20,37] of superior brightness have been reported, the dyad-type reversible fluorescence photoswitch typically employs a conventional and potentially safer small-molecule fluorescent dye as the FRET donor with relatively high molar absorptivity (e.g., cyanine [38] ). Thus, for a given DAE derivative (FRET acceptor), the performance of fluorescence photoswitching at the intended emission wavelength, as assessed by the on-off contrast, brightness, and fatigue resistance, can be improved by pairing with a fluorophore of, conceivably, better matching optical properties-e.g., absorption and emission maxima, Stokes shift, spectral bandwidth, molar absorptivity, and quantum yield.Fluorescence imaging [16,39] has been one of the most versatile and frequently used techniques in laboratories conducting experiments related to biology and medicine. Furthermore, in the clinical setting, the usage of fluorescence probes in the operation room can provide visual guidance for tissue inspection without the need for bulky and expensive instrumentation, potentially leading to substantially improved surgical outcomes. [40][41][42][43] Despite the benefits of simplicity, low cost, and Fluorescence imaging is an indispensable tool in modern biological research, allowing simple and inexpensive color-coded visualizations of real-time events in living cells and animals, as well as of fixed states of ex vivo specimens. The accuracy of fluorescence imaging in living systems is, however, impeded by autofluorescence, light scattering, and limited penetration depth of light. Nevertheless, the clinical use of fluorescence imaging is expected to grow along with advances in imaging equipment, and will increasingly demand high-accuracy probes to avoid ...
We report the case of a 56-year-old man who presented with dysphagia and weight loss. An esophagoduodenoscopy revealed a severe esophageal stricture in the distal esophagus. After surgical resection, the final pathologic analysis revealed that the tumor was comprised of benign-appearing fibroinflammatory cells with an increase and predominance of IgG4-positive plasma cells. He did not, however, have any other symptoms indicative of systemic autoimmune disease or connective tissue disorders. Histologically, abundant infiltration of IgG4-positive plasma cells and lymphocytes was observed. The patient was diagnosed with IgG4-related disease, definitive, with esophageal involvement.
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